CN106732691A - A kind of composite catalyst for organochlorine pollutant of degrading and preparation method thereof - Google Patents
A kind of composite catalyst for organochlorine pollutant of degrading and preparation method thereof Download PDFInfo
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- CN106732691A CN106732691A CN201710051746.9A CN201710051746A CN106732691A CN 106732691 A CN106732691 A CN 106732691A CN 201710051746 A CN201710051746 A CN 201710051746A CN 106732691 A CN106732691 A CN 106732691A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 100
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 60
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 59
- 230000000593 degrading effect Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 44
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims description 23
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 150000001243 acetic acids Chemical class 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 61
- 238000006731 degradation reaction Methods 0.000 abstract description 47
- 230000015556 catabolic process Effects 0.000 abstract description 46
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- LZQHZOIDAMYHSS-UHFFFAOYSA-N [F].[Ti] Chemical compound [F].[Ti] LZQHZOIDAMYHSS-UHFFFAOYSA-N 0.000 description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 238000011160 research Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003993 organochlorine pesticide Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009246 food effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 210000004251 human milk Anatomy 0.000 description 1
- 235000020256 human milk Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of composite catalyst of organochlorine pollutant of degrading, and belongs to degradation catalyst technical field.Composite catalyst of the present invention is by F TiO2The Fe constituted with zeroth order Fe0/F‑TiO2Composite catalyst.The Fe0/F‑TiO2Composite catalyst by including butyl titanate, ferric nitrate, hydrofluoric acid raw material, using sol-gal process by Fe3+Metal ion is carried on F TiO2On, drying, roasting, then through reduce method prepare.What the present invention was provided both has F TiO2Photocatalytic oxidation properties again with Zero-valent Iron fenton-type reagent performance Fe0/F‑TiO2, because being provided with photocatalysis and fenton-type reagent performance simultaneously, so as to strengthen the catalytic decomposition ability to organochlorine pollutant, the degradation rate to organochlorine pollutant can reach more than 90% for novel composite catalyst, the catalyst.
Description
Technical field
The invention belongs to degradation catalyst technical field, more particularly to a kind of catalysis degraded to organochlorine pollutant
Agent, specially a kind of composite catalyst for organochlorine pollutant of degrading and preparation method thereof.
Background technology
China is the first big organo-chlorine pesticide consumption and producing country in developing country, in the sixties to the eighties in 20th century
A large amount of agricultural chemicals mainly organo-chlorine pesticides for producing and using.The a large amount of use of organo-chlorine pesticide not only brings environmental pollution,
And human health is jeopardized, due to their Stability Analysis of Structures, bio-refractory, in the environment with high residue, they pass through
Biological concentration and the effect of food chain enter human body and animal body, can be accumulated in the tissue such as liver, kidney.Due to organochlorine pollutant
It is fat-soluble larger, so being accumulated in fat most.The remains of pesticide of accumulation can also be discharged by breast milk, or be transferred to the groups such as yolk
Knit, influence filial generation, and many organochlorine pollutants solubility in water is big, long half time.
Being reported first by Japanese Scientists since 1972 can be in TiO2By water photodissociation into H on electrode2And O2.Then, and
There is researcher successfully by TiO2For Degradation of Organo-pollutants in Water with Photo-catalysis.TiO2Itself have good chemical stability,
The characteristic such as abrasion resistance, resistance to photetching, inexpensive and nontoxic, therefore TiO2Photocatalysis technology is subject to countries in the world environmental energy research
The strong interest of person.Yet with Detitanium-ore-type TiO2It is wide bandgap semiconductor (Eg=3.2eV), the purple of short wavelength can only be responded
Outside line part (λ<387nm, account for solar energy 8%), and most of visible light part is accounted in solar spectrum, and (energy is accounted for
45%) effectively utilization is then failed.Therefore, TiO is caused by modification2Strengthen in the wavelength response of visible light part, can be efficiently
Solve the problems, such as that environmental energy turns into TiO using natural energy resources solar energy2One big focus of photocatalysis field research.Then have again
Scholar is linearly sewed by complete gesture plus plane wave model calculates C, N, F, P, S and replaces Detitanium-ore-type TiO respectively2During middle Lattice Oxygen
The density of states after find, nonmetal doping can make its energy gap reduce, so as to trigger visible-light response type nonmetal doping
TiO2The research of photochemical catalyst.
The eighties in 20th century, American scientist proposed to use zero-valent metal to reduce chlorinated organics pollutant first, using zero
The weak solution of valency iron deoxygenization chlorination aliphatic hydrocarbon.Then, scholar proposes the zero-valent iron technology that water body situ is repaired again.Due to zero
Valency metal low cost, is easy to get, at the same it is easy, effective using zero-valent metal reduction dechlorination degraded chlorinated organics, both at home and abroad at this
One field all expands some research work and achieves certain achievement, and zero-valent metal catalyst has obtained vast grinding in recent years
The favor of the person of studying carefully.
At present, Fluorin doped TiO is prepared2Method can be divided into sol-gel process, Hydrolyze method, hydro-thermal method, solvent-thermal method, spray
Mist pyrolysismethod, chemical vapor infiltration, electrochemical oxidation process and ion implantation.The material that although these methods are prepared is received
Rice corpuscles high-purity, particle diameter distribution are narrow, catalysis activity is good, but nearly all carry out at high temperature, and the requirement to equipment is high, from
And increased complexity, low yield, the high cost of preparation technology, and high-temperature roasting TiO2Particle crystal, easily causes particle
Reunite, reduce photocatalytic activity.However, the method for preparing Zero-valent Iron at present also has many kinds, for example：Microemulsion method.By metal
Molysite is added in microemulsion, in its water core microcell internal control glue grain nucleating growth, nanoparticle is obtained after heat treatment.With tradition side
Method is compared, and nano-particle prepared by the method is preparing nano metal particles side the features such as have even particle size distribution, good dispersion
There are very big potentiality in face, but relatively costly, and technique is complex.Vaporization condensation process.Physical vaporous deposition is also called, using true
The methods such as empty evaporation, LASER HEATING evaporation, electron beam irradiation, sputtering make material gasification or form plasma, and in media as well
Drastically condense.Nano zero valence iron purity prepared by this method is high, particle diameter is small, crystalline structure good, and easily controllable granularity, but agglomeration
Can be poor, high to technical equipment requirement, operation has danger.
The content of the invention
It is an object of the invention to provide a kind of Fe of organochlorine pollutant of degrading0/F-TiO2Composite catalyst and its preparation
Method.Using the chemical reaction characteristic of sol-gel process, make Fe3+Metal ion is carried on F-TiO2On, then by drying, true
Reduction obtains Fe after empty low-temperature bake0/F-TiO2Composite catalyst.Composite catalyst of the present invention both has F-TiO2Photocatalysis
Oxidation susceptibility has the fenton-type reagent performance of Zero-valent Iron again, so that strengthen the catalytic decomposition ability to organochlorine pollutant,
Improve its degradation rate.The object of the invention is realized by following technical proposals：
A kind of composite catalyst of organochlorine pollutant of degrading, the composite catalyst is by F-TiO2Constituted with zeroth order Fe
Fe0/F-TiO2Composite catalyst.
As an a kind of specific embodiment of the composite catalyst of organochlorine pollutant of degrading of the present invention, the Fe0/F-
TiO2Composite catalyst is by first by Fe3+Metal ion is carried on F-TiO2On, then through reduce method prepare.
As an a kind of specific embodiment of the composite catalyst of organochlorine pollutant of degrading of the present invention, the Fe0/F-
TiO2Composite catalyst by including butyl titanate, ferric nitrate, hydrofluoric acid raw material, using sol-gel process by Fe3+Metal ion
It is carried on F-TiO2On, drying, roasting, then through reduce method prepare.
Used as an a kind of specific embodiment of the composite catalyst of organochlorine pollutant of degrading of the present invention, the roasting exists
Carried out in vacuum, temperature is 100~400 DEG C；Using nitrogen protection, reducing agent is in sodium borohydride or potassium borohydride for the reduction
One or two.
The present invention also provides the preparation method of the composite catalyst of the degraded organochlorine pollutant, comprises the following steps：
1) preparation of solution A：To adding absolute ethyl alcohol in reaction vessel and being put into heating stirring in 30~50 DEG C of water-baths, delay
It is slow to add butyl titanate, it is then quickly added into glacial acetic acid and Fe (NO3)3, stir 25~35min, obtained solution A；
2) preparation of solution B：To adding hydrofluoric acid in absolute ethyl alcohol and distilled water, and with acid for adjusting pH to 2~4, it is obtained
Solution B；
3)Fe3+/F-TiO2The preparation of powder：Under 30~50 DEG C of water-bath, it is stirred vigorously and solution B is added drop-wise to solution A
In, 22~26h of ageing obtains gel, and Fe is obtained after drying, roasting3+/F-TiO2Powder；
4)Fe0/F-TiO2The preparation of composite catalyst：By Fe3+/F-TiO2Powder under nitrogen protection, is obtained final product through reduction
Fe0/F-TiO2Composite catalyst.
It is molten as an a kind of specific embodiment of the method for preparing composite catalyst of organochlorine pollutant of degrading of the present invention
In the preparation of liquid A, it is 25~35 that the absolute ethyl alcohol, butyl titanate, glacial acetic acid add volume ratio：5~15：1~6；The titanium
Ti and Fe (NO in acid butyl ester3)3The mass ratio of middle Fe is 0.01~0.2：1, Ti of the present invention are according to Zero-valent Iron with the mass ratio of Fe
Fenton-type reagent and F-TiO2Photocatalytic oxidation properties determine, can be by the range of the ferrotianium mass ratio of the present invention
Its oxidation synergy is performed to most preferably, and then it is most strong to reach its degradation to organochlorine pollutant, and degradation rate reaches
Most preferably；Ti and the mass ratio of Fe not in the range of the present invention is limited can influence Zero-valent Iron and F-TiO2Synergy, shadow
The composite catalyst for preparing is rung to the degradation of organochlorine pollutant, reduces degradation rate.
It is molten as an a kind of specific embodiment of the method for preparing composite catalyst of organochlorine pollutant of degrading of the present invention
In the preparation of liquid B, the absolute ethyl alcohol is 8~13 with the volume ratio of distilled water：3~6；F and butyl titanate in the hydrofluoric acid
The mol ratio of middle Ti is 1：0.01~0.8；The acid is one or two in concentrated nitric acid or hydrochloric acid.Titanium fluorine of the present invention mole
Than being the absorption property for fully taking into account composite catalyst to organochlorine pollutant, the aobvious acidity of hydrofluoric acid, its addition is excessive
Or it is very few can all influence organochlorine pollutant in the absorption property on composite catalyst surface, so as to influence composite catalyst to organic
The degradation property of cl contaminant, reduces degradation rate.
In addition, in the preparation of solution B, pH is limited into 2-4, under the conditions of this pH, metatitanic acid can be well controlled
The hydrolysis rate of butyl ester, so as to control TiO2Crystal formation, the performance of composite catalyzing is reached most preferably.When pH is not limited in the present invention
When in the range of system, the hydrolysis rate of butyl titanate is quickly, it is impossible to form gel state, cannot prepare of the invention being combined and urge
Agent.
As an a kind of specific embodiment of the method for preparing composite catalyst of organochlorine pollutant of degrading of the present invention, institute
It is 75~85 DEG C to state drying temperature, and the roasting condition is 5~8h of roasting in 100~400 DEG C of vacuum.It is of the invention compound with conventional
Method for preparing catalyst is compared, and is calcined using vacuum and low temperature, is to prevent Fe by sintering temperature control at 100~400 DEG C3+
Fe is easily formed in high temperature aerobic conditions2O3Or Fe3O4, further influence Fe3+Under nitrogen protection Zero-valent Iron is formed through reduction
Fe, so as to influence the structure of composite catalyst and the performance of catalyst, makes degradation rate reduction of the catalyst to organochlorine pollutant.
As an a kind of specific embodiment of the method for preparing composite catalyst of organochlorine pollutant of degrading of the present invention, institute
The volume ratio for stating absolute ethyl alcohol addition during absolute ethyl alcohol addition is prepared with solution B in prepared by solution A is 25~35：8~13.
As an a kind of specific embodiment of the method for preparing composite catalyst of organochlorine pollutant of degrading of the present invention, institute
The preparation of composite catalyst is stated, is comprised the following steps：
1) preparation of solution A：Take in the conical flask that 30ml absolute ethyl alcohols add 250ml, and conical flask is put into 40 DEG C of water
Heating stirring in bath；10ml butyl titanates are slowly added in the conical flask being stirred vigorously, 3ml glacial acetic acids are then quickly added into
With Fe (NO3)3, it is 0.01~0.2 to keep 40 DEG C of stirrings 30min, wherein obtained solution A, Ti and Fe mass ratioes；
2) preparation of solution B：10ml absolute ethyl alcohols, 5ml distilled water are taken in 50ml small beakers, the hydrofluoric acid for adding is used
It is 2 that concentrated nitric acid is adjusted to pH, is made solution B, wherein, the mol ratio of Ti and F is 0.01~0.8；
3)Fe3+/F-TiO2The preparation of powder：Under 40 DEG C of water-baths, it is stirred vigorously and solution B is added drop-wise in solution A, drips
Bi Hou, ageing 24h obtains gel, is placed in 80 DEG C of baking ovens and dries, and 5~8h is calcined in 100~400 DEG C of vacuum, is calcined
Fe afterwards3+/F-TiO2Powder；
4)Fe0/F-TiO2The preparation of composite catalyst：By Fe3+/F-TiO2Under nitrogen protection, through sodium borohydride reduction system
It is standby to obtain Fe0/F-TiO2Composite catalyst.
Additionally, it should declare, the reaction raw materials used by the present invention include absolute ethyl alcohol, butyl titanate, glacial acetic acid, distillation
Water, hydrofluoric acid etc. are added by the way of volume ratio, and its volume ratio is little on reaction or properties of product influence, as long as
Added using the convenient source mass fraction or purity of this area, this technical characteristic comes to those skilled in the art
Say it is obvious.
Beneficial effects of the present invention：
1st, the present invention provides a kind of both with F-TiO2Photocatalytic oxidation properties again with Zero-valent Iron Fenton-like oxygen
Change the Fe of performance0/F-TiO2Novel composite catalyst, the catalyst because be provided with photocatalysis and fenton-type reagent simultaneously
Can, so as to strengthen the catalytic decomposition ability to organochlorine pollutant, improve its degradation rate.
2nd, Fe of the present invention0/F-TiO2Novel composite catalyst the degradation rate of organochlorine pollutant can be reached 90% with
On.
3rd, the present invention makes Fe using the chemical reaction characteristic of sol-gel process3+Metal ion is carried on F-TiO2On, then
Fe is obtained by drying, roasting, reduction0/F-TiO2Composite catalyst；Its preparation method is simple, and roasting is carried out using vacuum,
Temperature is 100~400 DEG C, low for equipment requirements, easily operation, is reunited between particle few, can effectively prevent Fe3+It is aerobic in high temperature
Fe is formed in condition2O3Or Fe3O4, it is ensured that composite catalyst has the fenton-type reagent performance of Zero-valent Iron and to organochlorine dirt
Contaminate the degradation rate of thing.
Brief description of the drawings
Fig. 1 is the Fe that embodiment 2 is prepared when Ti and Fe mass ratioes are 0.20/F-TiO2The XPS of composite catalyst is composed entirely
Figure.
Fig. 2 is the Fe that embodiment 3 is prepared when Ti and F mol ratios are 0.20/F-TiO2The XRD of composite catalyst.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Fe of the present invention0/F-TiO2The preparation method of composite catalyst is as follows：
1st, the preparation of solution A：Take in the conical flask that 30ml absolute ethyl alcohols add 250ml, and conical flask is put into 40 DEG C of water
Heating stirring in bath；10ml butyl titanates are slowly added in the conical flask being stirred vigorously, 3ml glacial acetic acids are then quickly added into
With Fe (NO3)3, 40 DEG C of stirring 30min are kept, solution A is made, wherein Ti is 0.05 with Fe mass ratioes；
2nd, the preparation of solution B：10ml absolute ethyl alcohols, 5ml distilled water are taken in 50ml small beakers, hydrofluoric acid is added, with dense
It is 2 that nitric acid is adjusted to pH, is made solution B, wherein, Ti is 0.01 with F mol ratios；
3、Fe3+/F-TiO2The preparation of powder：Under 40 DEG C of water-baths, it is stirred vigorously and solution B is added drop-wise in solution A, is aged
24h obtains gel, is placed in 80 DEG C of baking ovens and dries, and is calcined 6h in 100 DEG C of vacuum, obtains Fe3+/F-TiO2Powder；
4、Fe0/F-TiO2The preparation of composite catalyst：By Fe3+/F-TiO2Fe is prepared through sodium borohydride reduction0/F-
TiO2Composite catalyst.
Photocatalytic degradation is carried out to 2,4,6- trichlorophenol, 2,4,6,-Ts：
By the Fe of the above-mentioned preparations of 0.05g0/F-TiO2Composite catalyst is added to 100ml, the 2 of 20mg/L, 4,6- trichloro-benzenes
30min being stirred in phenol solution, in dark reaction case and reaching adsorption equilibrium, optical filter (is used as visible light source with 400W metal halid lamps
Filter off the light of below 420nm), 2h is reacted, Filtration of catalyst, filtrate is concentrated with n-hexane extraction, using gas chromatograph
It is measured and calculates.Fe prepared by above-mentioned implementation method0/F-TiO2Degradation rate of the composite catalyst to 2,4,6- trichlorophenol, 2,4,6,-Ts
It is 90%.
Influence of the sintering temperature of embodiment 1 to composite catalyst degradation property
Roasting condition according to the form below 1 is modified, other steps are identical with above-mentioned preparation method, and it is right according to the method described above
2,4,6- trichlorophenol, 2,4,6,-Ts are degraded, influence of the research composite catalyst to organochlorine pollutant degradation property.
The degradation rate of composite catalyst under the different roasting conditions of table 1
As can be seen from Table 1, at a temperature of the vacuum condition that the present invention is limited and 100~400 DEG C, for preparing is compound
Catalyst reaches more than 90% to the degradation rate of organochlorine pollutant, but when being modified to roasting condition, by roasting temperature
The degradation property that degree reduced or increased the composite catalyst all to preparing has a significant impact, its degraded to organochlorine pollutant
Rate is reduced to 20~30%, because temperature is too low to influence TiO2The formation of crystal formation, temperature is too high to make TiO2Generation is reunited existing
As so the degradation rate that can all make organochlorine pollutant too high or too low for temperature is reduced.Roasting is changed into antivacuum, its degradation rate
41% is reduced to, under conditions of antivacuum, Fe3+Form be affected, so as to reduce the degraded to organochlorine pollutant
Rate.Illustrate that composite catalyst performance of the roasting condition of the present invention to preparing has a significant impact, in the roasting bar that the present invention is limited
Under part the degradation property of composite catalyst can significantly improve.
Should declare, the comparative example of the present embodiment is wherein to be carried out below or above the temperature outside roasting design temperature
Enumerate, and other temperature values not in the range of sintering temperature of the present invention can also reach identical technique effect, i.e., not at this
The composite catalyst prepared under invention sintering temperature also can only achieve 20~30% to the degradation rate of organochlorine pollutant, herein
Do not itemize.
Influence of the ferrotianium mass ratio of embodiment 2 to composite catalyst degradation property
Ferrotianium quality is modified than according to the form below 2, other steps are identical with above-mentioned preparation method, and according to the method described above
To 2,4,6- trichlorophenol, 2,4,6,-Ts are degraded, influence of the research composite catalyst to organochlorine pollutant degradation property.
The different ferrotianium mass ratioes of table 2 prepare the degradation rate of composite catalyst
As can be seen from Table 2, under the conditions of the ferrotianium mass ratio 0.01~0.2 that the present invention is limited, for preparing is compound
Catalyst reaches more than 90% to the degradation rate of organochlorine pollutant, but when being modified to ferrotianium mass ratio, is contracted
Hour, its composite catalyst prepared was reduced to 40% or so to the degradation rate of organochlorine pollutant, and this is the matter due to ferrotianium
Than reducing, the amount of iron excessively makes the excessively multipair F-TiO of the Zero-valent Iron after reduction to amount2A coating function has been carried out to have impact on to light
Absorb, so that degradation rate reduction.The composite catalyst that it is prepared when being increased drops to the degradation rate of organochlorine pollutant
It is low to 80% or so, this is very few influence its fenton-type reagent and the photocatalysis of content of iron because the mass ratio of ferrotianium increases
The synergy of oxidation, so that degradation rate is integrally reduced.Illustrate ferrotianium mass ratio of the present invention to the composite catalyst prepared
Performance has a significant impact, and can significantly improve the degradation property of composite catalyst under the ferrotianium mass ratio that the present invention is limited.
Should declare, the comparative example of the present embodiment is that the ratio being wherein below or above outside ferrotianium mass ratio is entered into ranks
Lift, and other can also reach identical technique effect without ferrotianium mass ratio within the scope of the present invention, i.e., less than titanium of the present invention
The composite catalyst that weight of iron is prepared than under also can only achieve 40% or so to the degradation rate of organochlorine pollutant, higher than this hair
The composite catalyst prepared under bright ferrotianium mass ratio also can only achieve 80% or so to the degradation rate of organochlorine pollutant, herein
Do not itemize.
Influence of the titanium fluorine mol ratio of embodiment 3 to composite catalyst degradation property
Titanium fluorine mol ratio according to the form below 3 is modified, other steps are identical with above-mentioned preparation method, and according to the method described above
To 2,4,6- trichlorophenol, 2,4,6,-Ts are degraded, influence of the research composite catalyst to organochlorine pollutant degradation property.
The different titanium fluorine mol ratios of table 3 prepare the degradation rate of composite catalyst
As can be seen from Table 3, under the conditions of the titanium fluorine mol ratio that the present invention is limited is as 0.01~0.8, for preparing answers
Close catalyst and more than 90% is reached to the degradation rate of organochlorine pollutant, but when being modified to titanium fluorine mol ratio, by it
The composite catalyst that it is prepared during diminution is reduced to 50% or so to the degradation rate of organochlorine pollutant, when the contracting of titanium fluorine mol ratio
Hour, the doping of fluorine is excessive, F-TiO2The acid too strong influence organochlorine pollutant on surface is in F-TiO2The absorption on surface so as to
Influence is to its degradation rate.The composite catalyst that it is prepared when being increased is reduced to 70% to the degradation rate of organochlorine pollutant
Left and right, when titanium fluorine mol ratio increases, the doping of fluorine is too small, makes F-TiO2Reduce in the absorption of visible region, so as to influence
Its degradation rate to organochlorine pollutant.Illustrate that composite catalyst performance of the titanium fluorine mol ratio of the present invention to preparing has very big shadow
Ring, can significantly improve the degradation property of composite catalyst under the titanium fluorine mol ratio that the present invention is limited.
Should declare, the comparative example of the present embodiment is that the ratio being wherein below or above outside titanium fluorine mol ratio is entered into ranks
Lift, and other can also reach identical technique effect without titanium fluorine mol ratio within the scope of the present invention, i.e., less than titanium of the present invention
The composite catalyst prepared under fluorine mol ratio also can only achieve 50% or so to the degradation rate of organochlorine pollutant, higher than this hair
The composite catalyst prepared under bright titanium fluorine mol ratio also can only achieve 70% or so to the degradation rate of organochlorine pollutant, herein
Do not itemize.
Fig. 1 is the Fe prepared when Ti and Fe mass ratioes are 0.2 in embodiment 20/F-TiO2The XPS of composite catalyst is composed entirely
Figure, knowable to the full spectrogram of Fig. 1 composite catalysts, the composite catalyst after doping occurs in that the peak position of F and Fe respectively, also contains
There is carbon, this is that, due to being polluted by the carbon in environment, residual on a catalyst, but does not influence the catalysis activity of catalyst.
Fig. 2 is the Fe prepared when Ti and F mol ratios are 0.2 in embodiment 30/F-TiO2The XRD of composite catalyst.By
Knowable to Fig. 2, Fe0/F-TiO2Composite catalyst maintains TiO2Crystalline form, while occurring in that the peak of Zero-valent Iron, illustrate this implementation
Fe prepared by example0/F-TiO2Composite catalyst both has F-TiO2Photochemical catalytic oxidation again with Zero-valent Iron fenton-type reagent
Performance.
Should declare, embodiment of the present invention 1-3 in the range of the present invention is limited under conditions of prepared Fe0/F-TiO2It is multiple
Closing catalyst all has and above-mentioned Fig. 1 and Fig. 2 composite catalysts identical structure and performance.Herein simply by embodiment 2 when
The Fe that Ti and Fe mass ratioes are prepared when being 0.20/F-TiO2In the full spectrograms of XPS and embodiment 3 of composite catalyst when Ti with F moles
Than for 0.2 when the Fe for preparing0/F-TiO2The XRD of composite catalyst is enumerated, and other are in the range of qualifications of the present invention
Fe prepared by embodiment0/F-TiO2Composite catalyst also has identical properity and effect.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (10)
1. it is a kind of degrade organochlorine pollutant composite catalyst, it is characterised in that the composite catalyst is by F-TiO2With zero
The Fe of valency Fe compositions0/F-TiO2Composite catalyst.
2. as claimed in claim 1 it is a kind of degrade organochlorine pollutant composite catalyst, it is characterised in that the Fe0/F-
TiO2Composite catalyst is by first by Fe3+Metal ion is carried on F-TiO2On, then through reduce method prepare.
3. as claimed in claim 2 it is a kind of degrade organochlorine pollutant composite catalyst, it is characterised in that the Fe0/F-
TiO2Composite catalyst by including butyl titanate, ferric nitrate, hydrofluoric acid raw material, using sol-gel process by Fe3+Metal ion
It is carried on F-TiO2On, drying, roasting, then through reduce method prepare.
4. as claimed in claim 3 it is a kind of degrade organochlorine pollutant composite catalyst, it is characterised in that the roasting is true
Carry out in the air, temperature is 100~400 DEG C；Using nitrogen protection, reducing agent is in sodium borohydride or potassium borohydride for the reduction
One or two.
5. a kind of preparation method of the composite catalyst of organochlorine pollutant of degrading as described in any one of Claims 1-4, it is special
Levy and be, comprise the following steps：
1) preparation of solution A：To adding absolute ethyl alcohol in reaction vessel and be put into heating stirring in 30~50 DEG C of water-baths, it is slow plus
Enter butyl titanate, be then quickly added into glacial acetic acid and Fe (NO3)3, stir 25~35min, obtained solution A；
2) preparation of solution B：To adding hydrofluoric acid in absolute ethyl alcohol and distilled water, and with acid for adjusting pH to 2~4, obtained solution
B；
3)Fe3+/F-TiO2The preparation of powder：Under 30~50 DEG C of water-bath, it is stirred vigorously and solution B is added drop-wise in solution A, it is old
Change 22~26h and obtain gel, Fe is obtained after drying, roasting3+/F-TiO2Powder；
4)Fe0/F-TiO2The preparation of composite catalyst：By Fe3+/F-TiO2Powder under nitrogen protection, Fe is obtained final product through reduction0/F-
TiO2Composite catalyst.
6. as claimed in claim 5 it is a kind of degrade organochlorine pollutant composite catalyst preparation method, it is characterised in that it is molten
In the preparation of liquid A, it is 25~35 that the absolute ethyl alcohol, butyl titanate, glacial acetic acid add volume ratio：5~15：1~6；The titanium
Ti and Fe (NO in acid butyl ester3)3The mass ratio of middle Fe is 0.01~0.2：1.
7. as claimed in claim 5 it is a kind of degrade organochlorine pollutant composite catalyst preparation method, it is characterised in that it is molten
In the preparation of liquid B, the absolute ethyl alcohol is 8~13 with the volume ratio of distilled water：3~6；F and butyl titanate in the hydrofluoric acid
The mol ratio of middle Ti is 1：0.01~0.8；The acid is one or two in concentrated nitric acid or hydrochloric acid.
8. as claimed in claim 5 it is a kind of degrade organochlorine pollutant composite catalyst preparation method, it is characterised in that institute
It is 75~85 DEG C to state drying temperature, and the roasting condition is 5~8h of roasting in 100~400 DEG C of vacuum.
9. as claimed in claim 5 it is a kind of degrade organochlorine pollutant composite catalyst preparation method, it is characterised in that institute
The volume ratio for stating absolute ethyl alcohol addition during absolute ethyl alcohol addition is prepared with solution B in prepared by solution A is 25~35：8~13.
10. as claimed in claim 5 it is a kind of degrade organochlorine pollutant composite catalyst preparation method, it is characterised in that
Comprise the following steps：
1) preparation of solution A：Take in the conical flask that 30ml absolute ethyl alcohols add 250ml, and conical flask is put into 40 DEG C of water-baths
Middle heating stirring；10ml butyl titanates are slowly added in the conical flask being stirred vigorously, 3ml glacial acetic acids and Fe is then quickly added into
(NO3)3, it is 0.01~0.2 to keep 40 DEG C of stirrings 30min, wherein obtained solution A, Ti and Fe mass ratioes；
2) preparation of solution B：10ml absolute ethyl alcohols, 5ml distilled water are taken in 50ml small beakers, the hydrofluoric acid for adding uses dense nitre
Acid regulation is 2 to pH, is made solution B, wherein, the mol ratio of Ti and F is 0.01~0.8；
3)Fe3+/F-TiO2The preparation of powder：Under 40 DEG C of water-baths, it is stirred vigorously and solution B is added drop-wise in solution A, completion of dropping
Afterwards, ageing 24h obtains gel, is placed in 80 DEG C of baking ovens and dries, and 5~8h is calcined in 100~400 DEG C of vacuum, after being calcined
Fe3+/F-TiO2Powder；
4)Fe0/F-TiO2The preparation of composite catalyst：By Fe3+/F-TiO2Under nitrogen protection, it is prepared into through sodium borohydride reduction
To Fe0/F-TiO2Composite catalyst.
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